Anion and cation combined collecting agent for aluminosilicate minerals in neutral environment and preparation method of anion and cation combined collecting agent
By preparing a combined collector of vegetable oleamide fatty acids and tetradecyltributylphosphonium chloride under neutral conditions, the limitations of traditional collectors under acidic conditions were overcome, resulting in improved flotation performance, reduced costs, and increased recovery rate and grade.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-03
- Publication Date
- 2026-03-10
AI Technical Summary
Traditional anion and cation collectors can only be used under acidic conditions, resulting in high costs, significant environmental pressure, and unstable flotation performance, making it difficult to maintain high recovery rates and grades in harsh environments.
Vegetable oleamide fatty acids and tetradecyltributylphosphonium chloride were used as a combined anion and cation collector. The collector was prepared in a neutral environment through esterification and extraction processes to enhance water solubility and mud resistance, thereby achieving the separation of quartz and aluminosilicate minerals.
In a neutral environment, the flotation recovery rate and grade are improved, production costs are reduced, and the problems of low temperature resistance and poor adaptability of traditional collectors are solved.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of mineral extraction technology and relates to a combined anion and cation collector for aluminosilicate minerals under neutral conditions and its preparation method. Background Technology
[0002] Anionic and cationic mixed collectors are commonly used collectors in the flotation of aluminosilicate minerals and play an irreplaceable role. However, they are used in an acidic environment with a pH of 2-3, which results in high acid treatment costs and significant environmental pressure. In addition, they are greatly affected by various factors such as temperature, water quality, and fine mud content. Under harsh flotation environments, it is difficult to maintain the stability of flotation performance, leading to a significant decrease in recovery rate and grade. Summary of the Invention
[0003] The purpose of this invention is to overcome the limitation that traditional anion and cation collectors can only be used under acidic conditions. It improves the low-temperature resistance, mud resistance and poor adaptability of mixed collectors, enhances their flotation performance, effectively improves flotation recovery rate and grade, and reduces production costs.
[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A combined cationic and anionic collector for aluminosilicate minerals under neutral conditions, characterized by being composed of the following raw materials in the indicated weight ratios: 2-5 parts of vegetable oleamide fatty acid collector and 4-10 parts of tetradecyltributylphosphonium chloride; wherein the vegetable oleamide fatty acid collector is prepared by the following method: Esterification reaction was carried out with vegetable oil fatty acids with iodine value of 80-140 and pentafluorophenol. The reaction condensing agent was 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate (HATU). The reaction product was extracted with dichloromethane as solvent, and the extracted product was the activated ester of fatty acid pentafluorophenol. (2) The activated ester of fatty acid pentafluorophenol reacts with sarcosine in dichloromethane. Triethylamine is added as a pH adjuster to adjust the pH to 10-12. After the reaction is complete, the mixture is poured into ice water and hydrochloric acid is added to adjust the pH to 2-4. After precipitation, the product plant oleamide fatty acid collector is obtained by filtration.
[0005] Furthermore, the fatty acids with an iodine value of 80-140 are one or a combination of rapeseed oil fatty acids, soybean oil fatty acids, peanut oil fatty acids, and sunflower seed oil fatty acids.
[0006] Furthermore, in step (1), the weight ratio of vegetable oil fatty acids, pentafluorophenol and HATU is 0.8-1.2:1-1.2:1-1.2.
[0007] Furthermore, in step (1), the esterification reaction temperature is 15-30℃ and the reaction time is 2-6h.
[0008] Furthermore, in step (2), the weight ratio of fatty acid pentafluorophenol activated ester to sarcosine is 0.8-1.2:1-1.1.
[0009] Furthermore, in step (2), the reaction temperature is 15-30℃ and the reaction time is 1-3h.
[0010] The chemical equations involved in the reaction process of this invention are as follows: The esterification equation for the reaction of fatty acids in vegetable oil with pentafluorophenol is as follows:
[0011] The reaction equation for pentafluorophenol ester and sarcosine is as follows:
[0012] A method for using a combined cationic and anionic collector for aluminosilicate minerals under neutral conditions, characterized by comprising the following steps: The magnetically separated quartz and aluminosilicate mineral mixture is mixed with water and then floated in a single-cell flotation machine. The flotation reagents are anionic collector oleamide fatty acid and cationic collector tetradecyltributylphosphonium chloride. The reagents are added separately in the same batch (to avoid direct interaction between the two reagents). After flotation, aluminosilicate mineral products and quartz mineral products are obtained.
[0013] Furthermore, the dosage of the anionic reagent is 200-500 g / t, and the dosage of the cationic reagent is 400-1000 g / t.
[0014] Furthermore, the flotation pulp concentration in the flotation machine is 20-30%, the flotation pH is 7, the stirring time is 1-3 minutes, and the skimming time is 1-3 minutes.
[0015] Furthermore, the flotation temperature is 3-30℃.
[0016] Mixed collectors are classified into anionic and cationic collectors. Anionic fatty acid collectors typically exhibit improved flotation performance but significantly decreased water solubility with increasing carbon chain length. This invention utilizes a novel vegetable oil-based amide fatty acid as the anionic reagent, employing common and inexpensive vegetable oils such as soybean oil, rapeseed oil, and peanut oil as raw materials. By introducing amide groups (reacting with pentafluorophenol and HATU, using dichloromethane as a solvent, extracting the active ester of the vegetable oil fatty acid, adding sarcosine for further reaction, and finally adding hydrochloric acid to crystallize the final product, the vegetable oil-based amide fatty acid), the water solubility and mud resistance of the anionic collector are enhanced. Furthermore, the improved water solubility allows for a further increase in the collector's carbon chain length, thus improving flotation performance. The cationic reagent uses tetradecyltributylphosphonium chloride. The combined use of these two reagents enables the flotation separation of quartz and aluminosilicate minerals under neutral conditions.
[0017] The beneficial effects of this invention are: 1. It uses common and inexpensive vegetable oils such as soybean oil, rapeseed oil, and peanut oil as raw materials, and the preparation method is simple and the raw materials are readily available; 2. This invention uses pentafluorophenol to activate carboxyl groups and promote the formation of amide groups. The synthesized vegetable oleamide fatty acid collector has both carboxyl and amide groups, which solves the problems of low temperature resistance, mud resistance and adaptability of traditional fatty acid collectors such as oleic acid. 3. The aluminosilicate mineral anion and cation combined collector provided by this invention can be used in a neutral environment and has better flotation performance than traditional fatty acid collectors such as oleic acid plus dodecylamine, which can effectively improve flotation recovery rate and grade. Detailed Implementation
[0018] A method for preparing and using a combined cationic and anionic collector for aluminosilicate minerals under neutral conditions, the specific implementation steps of which are as follows: Example 1
[0019] 1) Take 150g of rapeseed oil fatty acid with an iodine value of 100, 150g of pentafluorophenol and 220g of HATU and mix them in a beaker. React at 20℃ for 4h. Then use 2L of dichloromethane as a solvent to extract 250g of rapeseed oil fatty acid pentafluorophenol activated ester. 2) Mix 50g of rapeseed oil fatty acid pentafluorophenol activated ester and 50g of sarcosine in a beaker, add 100g of dichloromethane to fully dissolve the two, add triethylamine until the pH is 12, and control the temperature at 20℃ for 2 hours. 3) After the reaction is complete, pour all the substances in the beaker into ice water, add 30% hydrochloric acid solution dropwise until the pH is 3, rapeseed oil type amide fatty acid crystals precipitate, filter with medium-speed quantitative filter paper to obtain the final product rapeseed oil type amide fatty acid collector. 4) Magnetic concentrate (main components: SiO2 95.54%, Al2O3 2.02%, K2O 1.14%, Na2O 0.41%, Fe2O3 0.24%) from a glass production line in Inner Mongolia was mixed with water and floated in a single-cell flotation machine. The flotation reagents used were anionic collector vegetable oleamide fatty acid and cationic collector tetradecyltributylphosphonium chloride. The reagents were added separately in the same batch (to avoid direct interaction between the two reagents). During the flotation process, the flotation pulp concentration was 25%, the flotation pH was 7, the anionic collector dosage was 400 g / t, the cationic collector dosage was 800 g / t, the stirring time was 2 min, and the skimming time was 3 min. After flotation, aluminosilicate mineral products and quartz mineral products were obtained. Example 2
[0020] 1) Take 147g of rapeseed oil fatty acid with an iodine value of 110, 160g of pentafluorophenol and 220g of HATU and mix them in a beaker. React at 20℃ for 4h. Then use 2L of dichloromethane as a solvent to extract 250g of rapeseed oil fatty acid pentafluorophenol activated ester. 2) Mix 52g of rapeseed oil fatty acid pentafluorophenol activated ester and 50g of sarcosine in a beaker, add 97g of dichloromethane to fully dissolve the two, add triethylamine until the pH is 12, and control the temperature at 20℃ for 2 hours. 3) After the reaction is complete, pour all the substances in the beaker into ice water, add 30% hydrochloric acid solution dropwise until the pH is 3, rapeseed oil type amide fatty acid crystals precipitate out, filter with medium-speed quantitative filter paper to obtain the final product rapeseed oil type amide fatty acid collector.
[0021] 4) Magnetic concentrate (main components: SiO2 95.54%, Al2O3 2.02%, K2O 1.14%, Na2O 0.41%, Fe2O3 0.24%) from a glass production line in Inner Mongolia was mixed with water and floated in a single-cell flotation machine. The flotation reagents used were anionic collector vegetable oleamide fatty acid and cationic collector tetradecyltributylphosphonium chloride. The reagents were added separately in the same batch (to avoid direct interaction between the two reagents). During the flotation process, the flotation pulp concentration was 28%, the flotation pH was 7, the anionic collector dosage was 400 g / t, the cationic collector dosage was 800 g / t, the stirring time was 2 min, and the skimming time was 3 min. After flotation, aluminosilicate mineral products and quartz mineral products were obtained. Example 3
[0022] 1) Take 145g of rapeseed oil fatty acid with an iodine value of 110, 150g of pentafluorophenol and 220g of HATU and mix them in a beaker. React at 20℃ for 4h. Then use 2L of dichloromethane as a solvent to extract 250g of activated ester of rapeseed oil fatty acid pentafluorophenol. 2) Mix 50g of rapeseed oil fatty acid pentafluorophenol activated ester and 50g of sarcosine in a beaker, add 105g of dichloromethane to fully dissolve the two, add triethylamine until the pH is 12, and control the temperature at 20℃ for 2h. 3) After the reaction is complete, pour all the substances in the beaker into ice water, add 30% hydrochloric acid solution dropwise until the pH is 3, rapeseed oil type amide fatty acid crystals precipitate out, filter with medium-speed quantitative filter paper to obtain the final product rapeseed oil type amide fatty acid collector.
[0023] 4) Magnetic concentrate (main components: SiO2 95.54%, Al2O3 2.02%, K2O 1.14%, Na2O 0.41%, Fe2O3 0.24%) from a glass production line in Inner Mongolia was mixed with water and floated in a single-cell flotation machine. The flotation reagents used were anionic collector vegetable oleamide fatty acid and cationic collector tetradecyltributylphosphonium chloride. The reagents were added separately in the same batch (to avoid direct interaction between the two reagents). During the flotation process, the flotation pulp concentration was 30%, the flotation pH was 7, the anionic reagent dosage was 500 g / t, the cationic reagent dosage was 900 g / t, the stirring time was 2 min, and the skimming time was 3 min. After flotation, aluminosilicate mineral products and quartz mineral products were obtained. Comparative Examples
[0024] The rapeseed oil-based amide fatty acid collectors prepared in Examples 1-3 of this invention, combined with tetradecyltributylphosphonium chloride, were used in the flotation separation test of quartz feldspar in desert sand in Inner Mongolia. The comparative test results are shown in the table below:
Claims
1. A combination collector of anionic and cationic species of aluminosilicate minerals in a neutral environment, characterized in that The plant oil amide fatty acid collector is prepared by the following steps: The plant oil amide fatty acid collector is prepared by the following steps: The plant oil amide fatty acid collector is prepared by the following steps:
2. The combination collector of cations and anions of aluminosilicate minerals in a neutral environment according to claim 1, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
3. The combination collector reagent of cations and anions of aluminosilicate minerals in a neutral environment according to claim 1, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
4. The combination collector reagent of cations and anions of aluminosilicate minerals in a neutral environment according to claim 1, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
5. The combination collector agent of cations and anions of aluminosilicate minerals in a neutral environment according to claim 1, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
6. The combination collector agent of cations and anions of aluminosilicate minerals in a neutral environment according to claim 1, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
7. The use of a combination of cations and anions of aluminosilicate minerals in a neutral environment as a collector according to any one of claims 1 to 6, characterized in that The plant oil amide fatty acid collector is prepared by the following steps: The plant oil amide fatty acid collector is prepared by the following steps:
8. A method of using the combination of cations and anions of aluminosilicate minerals in a neutral environment according to claim 7, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
9. A method of using the combination of cations and anions of aluminosilicate minerals in a neutral environment according to claim 7, characterized by: The plant oil amide fatty acid collector is prepared by the following steps:
10. 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